KR101674703B1 - Method for forming reversed pattern and polysiloxane resin composition - Google Patents

Abstract

The present invention relates to a polysiloxane resin composition for forming an inverted pattern which is not mixed with a mask pattern formed on a substrate to be processed, can be favorably embedded in the gap of the mask pattern, excellent in dry etching resistance and storage stability, And a method for forming the same. (1) a mask pattern forming step of forming a mask pattern on a substrate to be processed; (2) an embedding step of embedding a polysiloxane resin composition in the gap of the mask pattern; and (3) Wherein the polysiloxane resin composition comprises an [A] polysiloxane having a specific structure and an organic solvent [B] having a specific structure, wherein the polysiloxane resin composition comprises an inverted pattern forming process to be.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polysiloxane resin composition,

The present invention relates to a reversal pattern forming method and a polysiloxane resin composition.

BACKGROUND ART [0002] In the pattern formation at the time of manufacturing a semiconductor device or the like, a new micropatterning of a substrate made of an organic material or an inorganic material has been proposed by an inversion pattern forming method using a lithography technique, an etching technique or the like (see Patent Document 1).

However, since the mask pattern formed on the substrate to be processed becomes finer as the degree of integration of the semiconductor device or the like in the circuit board progresses, and the volume of the gap of the pattern becomes smaller, It is difficult to embed in the gap of the mask pattern formed on the substrate to be processed satisfactorily as the pattern forming material. For this reason, there is a demand for a material for forming an inverse pattern which has better filling property. In addition, it is required that such a material for forming an inverse pattern should not be intermixed with a mask pattern formed on a substrate to be processed, and is required to have excellent dry etching resistance and storage stability. In addition, A resin composition has not yet been proposed.

Japanese Patent Application Laid-Open No. 2002-110510

An object of the present invention is to provide an inversion pattern forming method which can be well filled in the gap of the mask pattern without being mixed with a mask pattern formed on a substrate to be processed, .

According to an aspect of the present invention,

(1) a mask pattern forming step of forming a mask pattern on a substrate to be processed,

(2) an embedding step of embedding the polysiloxane resin composition in the gap of the mask pattern, and

(3) an inversion pattern forming step of removing the mask pattern to form an inversion pattern

The method comprising the steps of:

Wherein the polysiloxane resin composition comprises:

(A) a hydrolyzable silane compound represented by the following formula (1) (hereinafter also referred to as "compound (1)") and a hydrolyzable silane compound represented by the following formula (2) ) (Hereinafter also referred to as "[A] polysiloxane") obtained by hydrolysis and condensation of at least one member selected from the group consisting of

[B] An organic solvent (hereinafter also referred to as "[B] organic solvent") containing a compound represented by the following formula (3) (hereinafter also referred to as "

Wherein the reversal pattern forming method comprises the steps of:

≪ Formula (1) >

(Wherein R is a hydrogen atom, a fluorine atom, a straight or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group or an aryl group, An atom or -OR ¹ , R ¹ is a monovalent organic group, and a is an integer of 1 to 3, provided that when a plurality of R and X are present, they may be the same or different from each other)

≪ Formula (2) >

(In the formula (2), X is synonymous with the above formula (1)).

≪ Formula (3) >

(3), R 'is a linear or branched alkyl group having 1 to 10 carbon atoms, R' 'is a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, provided that R' The sum of the carbon numbers of R "is 4 to 10)

According to the inversion pattern forming method of the present invention, the polysiloxane resin composition for forming the reversal pattern is not intermixed with the mask pattern previously formed by the commonly used radiation-sensitive resin composition, and is favorably buried in the gap of the mask pattern . The reversed pattern formed by the present invention is also excellent in dry etching resistance. The term "mask pattern" means that the substrate is partially coated with a predetermined pattern. For example, a line-and-space pattern, a hole pattern, and the like are mentioned.

It is preferable that [A] the polysiloxane is a polysiloxane obtained by hydrolyzing and condensing the hydrolyzable silane compound represented by the above formula (1) and the hydrolyzable silane compound represented by the above formula (2).

If the polysiloxane [A] is a hydrolysis-condensation product of the compound (1) and the compound (2), the resin composition for forming the reversal pattern is excellent in the filling property between the mask patterns formed earlier by the generally used radiation- And the reversal pattern formed by the present invention is superior to the dry etching resistance.

It is preferable that X in the formulas (1) and (2) is -OR ¹ . Provided that R ¹ is as defined in the above formula (1).

When X in the formulas (1) and (2) is -OR ¹ , the resin composition for forming the reversal pattern has good filling property between the mask patterns previously formed by the radiation- The reversal pattern formed by the present invention is also superior in dry etching resistance.

The content of silicon atoms measured by the SIMS method of the formed reversed pattern is 30 mass% or more and 46.7 mass% or less, and the content of carbon atoms is 1 mass% or more and 50 mass% or less. When the element composition is within the above range, the obtained reversed pattern is excellent in dry etching resistance, and the surface of the coating film can be easily planarized.

(1) The mask pattern forming step comprises:

(i) a coating film forming step of forming a coating film by applying and drying a radiation-sensitive resin composition on a substrate to be processed,

(ii) an exposure step of irradiating a predetermined region on the coating film with radiation, and

(iii) a developing step of developing the exposed coating film

.

(ii) the exposure step is carried out continuously a plurality of times. According to the inversion pattern forming method of the present invention, it is possible to form an inversion pattern even in a gap of a finer mask pattern formed by the double exposure or the like.

(1) It is preferable that the mask pattern forming step is repeatedly performed so as to have the first mask pattern forming step and the second mask pattern forming step different from the first mask pattern. According to the inversion pattern forming method of the present invention, it is possible to form an inversion pattern well even in a gap of a finer mask pattern obtained by the double patterning.

The polysiloxane resin composition of the present invention

[A] a polysiloxane obtained by hydrolyzing and condensing at least one member selected from the group consisting of a hydrolyzable silane compound represented by the following formula (1) and a hydrolyzable silane compound represented by the following formula (2), and

[B] an organic solvent containing a compound represented by the following formula (3)

. ≪ / RTI >

≪ Formula (1) >

(Wherein R is a hydrogen atom, a fluorine atom, a straight or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group or an aryl group, An atom or -OR ¹ , R ¹ is a monovalent organic group, and a is an integer of 1 to 3. Furthermore, when a plurality of R 1 and X 2 are present, they may be the same or different from each other)

≪ Formula (2) >

(In the formula (2), X is synonymous with the above formula (1)).

≪ Formula (3) >

(3), R 'is a linear or branched alkyl group having 1 to 10 carbon atoms, R' 'is a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, provided that R' The sum of the carbon numbers of R "is 4 to 10)

The polysiloxane resin composition of the present invention can be preferably used for forming an inverted pattern. The polysiloxane resin composition is also excellent in storage stability.

The polysiloxane [A] is preferably a polysiloxane obtained by hydrolytic condensation of the hydrolyzable silane compound represented by the formula (1) and the hydrolyzable silane compound represented by the formula (2). When the polysiloxane [A] has the above specific structure, the polysiloxane resin composition is more excellent in storage stability and the like.

It is preferable that the weight average molecular weight in terms of polystyrene by size exclusion chromatography of [A] polysiloxane is 2,000 or more and 100,000 or less. If the [A] polysiloxane is the above-mentioned size, the polysiloxane resin composition is more excellent in storage stability and the like.

It is preferable to further contain a [C] curing accelerator. The curing of the polysiloxane embedded in the gaps of the mask pattern proceeds at a low temperature by applying the curing accelerator, thereby alleviating the firing conditions after the filling so that the transfer shape can be kept better.

The reversal pattern forming method and the polysiloxane resin composition of the present invention are capable of suppressing mixing with the mask pattern formed on the substrate to be processed, being well filled in the gap of the mask pattern, and being excellent in dry etching resistance and storage stability . Therefore, the present invention can be very advantageously used for the production of LSI which is expected to be further miniaturized in the future, particularly for the formation of fine contact holes and the like.

1 is a schematic diagram for explaining a method of forming an inversion pattern.

Hereinafter, embodiments of the present invention will be described in detail.

≪ Method of Forming Inversion Pattern >

(1) a mask pattern forming step (hereinafter also referred to as "step (1)") for forming a mask pattern on a substrate to be processed;

(2) an embedding step (hereinafter also referred to as "step (2)") for embedding the polysiloxane resin composition in the gap of the mask pattern, and

(3) an inverse pattern forming step (hereinafter also referred to as "step (3)") for forming an inverse pattern by removing the mask pattern,

Respectively. Each step will be described in detail below.

[Step (1)]

In this step, a mask pattern is formed on the substrate to be processed. The method of forming the mask pattern is not particularly limited, and can be formed using a known photolithography process. For example,

(i) a coating film forming step of applying a radiation-sensitive resin composition on a substrate to be processed and drying to form a coating film,

(ii) an exposure step of irradiating a predetermined area on the coating film with radiation, and

(iii) a developing step of developing the exposed coating film.

As the substrate to be processed in the step (i), for example, a silicon wafer, aluminum, copper, a wafer partially coated with silicon dioxide, or the like can be used. In order to maximize the potential of the radiation-sensitive resin composition to be described later on the substrate to be processed, an organic or inorganic antireflection film is formed on the surface of the substrate in advance, as disclosed in Japanese Patent Application Laid-Open No. 6-12452 .

As the radiation-sensitive resin composition, for example, a chemically amplified resist composition containing an acid generator or the like is dissolved in an appropriate solvent so as to have a solid content concentration of, for example, 0.1 to 20 mass% For example, a filter manufactured by filtering with a filter having a pore size of about 30 nm can be used. A commercially available resist composition such as a resist composition for ArF or a resist composition for KrF may be used as it is. Further, the radiation-sensitive resin composition may be a positive type or a negative type.

The method of applying the radiation sensitive resin composition is not particularly limited, and examples thereof include suitable coating means such as rotational coating, soft coating and roll coating. The drying means after applying the radiation sensitive resin composition is not particularly limited, but the solvent in the coating film can be volatilized by, for example, preliminary heating. The heating conditions are appropriately adjusted according to the composition of the radiation-sensitive resin composition, and are usually about 30 to 200 ° C, preferably 50 to 150 ° C. The thickness of the coating film obtained after drying is not particularly limited, but is usually 10 to 1000 nm, preferably 50 to 500 nm.

Examples of the radiation used in the exposure in the step (ii) include visible rays, ultraviolet rays, ultraviolet rays, EUV (ultraviolet rays), X-rays, charged particle rays And is preferably a deep ultraviolet ray represented by an ArF excimer laser (wavelength: 193 nm) or a KrF excimer laser (wavelength: 248 nm). EUV may also be used for the production of the fine mask pattern. The exposure conditions such as the exposure dose are appropriately selected according to the composition of the radiation sensitive resin composition and the kind of the additives. In addition, the exposure process may be performed through a mask having a predetermined design pattern. Further, it is preferable to perform the heat treatment after the exposure. By the heat treatment, the dissociation reaction of the acid dissociable group in the resin component can proceed smoothly. The heating conditions are appropriately selected according to the composition of the composition of the radiation-sensitive resin composition, and the heating temperature is usually 30 to 200 占 폚, preferably 50 to 170 占 폚. The heating time is usually 10 to 300 seconds, preferably 30 to 180 seconds.

Examples of the developer used in the development in the step (iii) include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, Diazabicyclo- [5.4.0] -7- (tert-butoxycarbonylamino) propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, Undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and the like, water, organic solvents and mixtures thereof. Of these, an alkaline aqueous solution is preferable. In addition, a proper amount of a surfactant or the like may be added to the developer containing the alkaline aqueous solution. Further, after development with a developer containing an alkaline aqueous solution, it is generally washed with water and dried.

The size of the mask pattern obtained in the step (1) (for example, the line width in the case of a line-and-space pattern, the hole diameter in the case of a hole pattern, etc.) is usually 10 to 100 nm. In addition, for example, a fine mask pattern of 10 to 30 nm can be formed by immersion exposure or the like.

Examples of the immersion liquid used for exposure include water and hydrocarbon-based inert liquids. In particular, when the exposure light source is an ArF excimer laser light (wavelength: 193 nm), it is preferable that the liquid immersion liquid is transparent to the exposure wavelength and that the temperature coefficient of the refractive index is as small as possible so as to minimize the distortion of the optical image projected onto the film. In addition to the above-described aspects, it is preferable to use water in terms of availability and ease of handling. In the case of using water, an additive for increasing the surface activity and reducing the surface tension of water may be added in a small proportion. It is preferable that this additive can neglect the influence of the lower surface of the lens on the optical coating without dissolving the coating layer on the wafer. Distilled water is preferred as the water to be used.

In the step (1), double exposure and double patterning may also be used.

The double exposure is a method in which, in the step (ii) after the step (i), the exposure with the mask of the desired design pattern is performed twice or more. In this case, the exposure is preferably performed continuously. For example, the first reduced projection exposure is performed through a line-and-space pattern mask in a desired area, and then the second reduced projection exposure is performed so that the lines intersect with the latent image of the line pattern formed by the first exposure, And performs reduction projection exposure. According to this exposure method, in the case of the positive radiation-sensitive resin composition, a columnar (columnar) mask pattern can be formed in the unexposed portion surrounded by the exposed portion.

The exposure for the plurality of times may use the same light source or use another light source, but it is preferable to use ArF excimer laser light for the first exposure.

The double patterning refers to (1) a mask pattern forming process having a step of forming a first mask pattern and a step of forming a second mask pattern different from the first mask pattern, by repeating the mask pattern forming process.

The first mask pattern forming step refers to a step (1) of forming a mask pattern on the substrate by the steps (i) to (iii) in the mask pattern forming step. The step of forming the second mask pattern means a step of forming a mask pattern different from the first pattern by the steps (i) to (iii) in the mask pattern forming step after forming the first mask pattern It says. In this case, the second mask pattern includes a case where the second mask pattern is formed at a different position through a mask having the same design pattern as that of the first mask pattern. The present invention also includes the case where the first mask pattern and the second mask pattern are formed in the same area through a mask having a different design pattern.

The first mask pattern formed by the steps (i) to (iii) in the mask pattern forming step (1) is preferably subjected to the insolubilization treatment to the radiation-sensitive resin composition for forming the second mask pattern Do. Examples of the insolubilization treatment include baking treatment and / or irradiation with a first mask pattern at a temperature of 120 占 폚 or higher, preferably 140 占 폚 or higher, preferably irradiation with light of a wavelength of 300 nm or shorter have. More specific exposing conditions include irradiation with radiation at an exposure dose of 2 to 20 times the optimum exposure amount for forming the first mask pattern. As a heating condition, a method of heating under a temperature condition higher than the temperature of post exposure baking (PEB), which is a post-exposure heating process at the time of forming the first mask pattern, is exemplified.

The insoluble resin composition may be coated on the surface of the first mask pattern and cured by baking or exposure to form an insoluble film. Examples of the insoluble resin composition include those having a property of containing a resin having a hydroxyl group and an alcohol solvent and insolubilized by baking. Specifically, examples thereof include a resin composed of a monomer having an amide bond in a molecule and a monomer having a hydroxyl group, a monohydric alcohol having 1 to 8 carbon atoms, and, if necessary, a crosslinking component. The insoluble first mask pattern can be formed by applying the insoluble resin composition, baking or exposing, and then, if necessary, cleaning the residual composition.

These insolubilization treatments may be performed only one kind or two or more kinds.

The second mask pattern can be formed by applying the radiation-sensitive resin composition on the substrate on which the first mask pattern is formed and by the same method as the above (1) step (i) to (iii) in the mask pattern forming step have. As described above, since the first mask pattern is inactivated or insolubilized, the mixing of the radiation sensitive resin composition for forming the second mask pattern and the first mask pattern does not occur. For example, by forming the second mask pattern in the space portion of the first mask pattern, a finer mask pattern can be formed.

With this method, it is possible to make the mask pattern finer in both the line-and-space pattern and the hole pattern.

[Step (2)]

In this step, a polysiloxane resin composition for forming an inverted pattern is embedded in the gap of the mask pattern. Specifically, the polysiloxane resin composition of the present invention is applied onto the substrate to be processed on which the mask pattern is formed by the appropriate application means such as spin coating, soft coating, roll coating, and the like, And is buried in the gap. The polysiloxane resin composition of the present invention used in this step (2) will be described later in detail.

In this step, it is preferable to provide a drying step after the polysiloxane resin composition is embedded in the gap of the mask pattern. The drying means is not particularly limited, but it is possible to volatilize the organic solvent in the composition by, for example, firing. The firing conditions are suitably adjusted according to the composition of the resin composition, but the firing temperature is usually 80 to 250 占 폚, preferably 80 to 200 占 폚. When the firing temperature is 80 to 180 占 폚, the planarization process, particularly the planarization process by the wet etch back process, which will be described later, can be performed smoothly. The heating time is usually 10 to 300 seconds, preferably 30 to 180 seconds. The thickness of the pattern anti-reflective resin film obtained after drying is not particularly limited, but is usually 10 to 1000 nm, preferably 50 to 500 nm.

[Step (3)]

In this step, the mask pattern is removed and an inverted pattern is formed. Specifically, first, the flattening process for exposing the upper surface of the mask pattern is preferably performed. Next, the mask pattern is removed by dry etching or dissolution removal, and a predetermined reverse pattern is obtained. As the planarization method used in the planarization, an etching method such as a dry etch-back or wet etch-back method, a CMP method, or the like can be used. Among these, a dry etch-back method and a wet etch-back method using a fluorine-based gas are preferable because the cost is low. The processing conditions in the planarization process are not particularly limited and can be suitably adjusted. Dry etching is preferable for removing the mask pattern, and more specifically, oxygen etching, ozone etching, and the like are preferably used. For the dry etching, a known resist stripping apparatus such as an oxygen plasma ashing apparatus or an ozone ashing apparatus can be used. The etching processing conditions are not particularly limited and can be suitably adjusted.

Hereinafter, a specific example of the reversal pattern forming method of the present invention having the steps (1), (2), and (3) will be described with reference to FIG.

1 (a), the radiation-sensitive resin composition is coated on the substrate 1 on which the antireflection film 2 is formed, and is subjected to a drying process such as heating to form a predetermined A coating film 3 of a film thickness is formed. The mask pattern 31 is formed by performing exposure by irradiation with radiation or the like through a mask having a predetermined design pattern and then developing it in a small area of the coating film 3 (see FIG. 1 (b)) .

Next, in the step (2), as shown in Fig. 1 (c), on the substrate 1 on which the mask pattern 31 is formed so that the resin composition is embedded in the gap of the mask pattern 31, The composition is applied, and the pattern anti-exclusive resin film 4 is formed through a drying process such as heating.

Thereafter, in the step (3), planarization is performed by an etch-back method or a CMP method so that the upper surface of the coating film 3 is exposed as shown in Fig. 1 (d). Next, the mask pattern 31 is removed by dry etching, whereby an inversion pattern 41 is formed (see Fig. 1 (e)).

The reversal pattern obtained by the reversal pattern forming method of the present invention preferably has a silicon atom content of 30 mass% or more and 46.7 mass% or less, more preferably 40 mass% or more and 46.7 mass% or less, as measured by the SIMS method. The content of carbon atoms is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less. If the silicon atom content is less than 30 mass%, resistance to dry etching using oxygen gas and ozone gas may be reduced. Further, when the content of silicon atoms exceeds 46.7 mass% or when the content of carbon atoms is less than 1 mass%, the storage stability of the polysiloxane may be extremely lowered.

For reference, the element composition of the silicon dioxide film measured by the SIMS method is 46.75 mass% of silicon atoms, 53.25 mass% of oxygen atoms, and 0 mass% of carbon atoms.

≪ Polysiloxane resin composition >

The polysiloxane resin composition of the present invention contains [A] a polysiloxane and [B] an organic solvent. And a [C] curing accelerator as a preferable component. And may contain other arbitrary components as long as the effect of the present invention is not impaired. The polysiloxane resin composition of the present invention is particularly preferably used in the reversed pattern forming method of the present invention described above, but is preferably used for an interlayer insulating film material, an antireflection film material, and a flat fire for planarizing a substrate. Each component will be described in detail below.

<[A] Polysiloxane>

The polysiloxane [A] is obtained by hydrolysis and condensation of at least one member selected from the group consisting of the compound (1) represented by the formula (1) and the compound (2) represented by the formula (2) Each of the compounds (2) may be used as one kind or a mixture of several kinds.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R in the above formula (1) include straight chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl and n-pentyl; A branched alkyl group such as an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, or an isoamyl group. In addition, some or all of hydrogen atoms contained in these alkyl groups may be substituted with a fluorine atom or the like.

Examples of the cyanoalkyl group include a cyanoethyl group and a cyanopropyl group.

Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.

As the alkenyl group, a group represented by the following formula (4) is preferable.

&Lt; Formula (4) >

(In the formula (4), n is an integer of 0 to 4)

In the above formula (4), n is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

Examples of the alkenyl group other than the group represented by the formula (4) include a 1-butenyl group, a 1-pentenyl group and a 1-hexenyl group.

Examples of the aryl group include phenyl, naphthyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, fluorophenyl, benzyl, phenethyl and methoxyphenyl.

X in the formulas (1) and (2) is preferably a halogen atom such as a fluorine atom or a chlorine atom, or -OR ¹ , and is preferably -OR ¹ . Examples of the monovalent organic group for R ¹ include an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- An aryl group such as a phenyl group, and a silyl group such as a dimethylsilyl group. In Formula (1), a is an integer of 1 to 3, preferably 1 or 2.

Specific examples of the compound (1) represented by the formula (1) include, for example, phenyltrimethoxysilane, benzyltrimethoxysilane, phenethyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-phenoxyphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, But are not limited to, methoxysilane, 4-acetylaminophenyltrimethoxysilane, 3-methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane , 3-hydroxyphenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 3-dimethylaminophenyltrimethoxysilane, 3-acetylaminophenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2- Ethylphenyltrimethoxysilane, 2-methoxyphenyltrimethoxysilane, 2-phenoxyphenyltrimethoxysilane, 2 -Hydroxyphenyltrimethoxysilane, 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2-acetylaminophenyltrimethoxysilane, 2,4,6-trimethylphenyltrimethoxysilane , 4-methylbenzyltrimethoxysilane, 4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 4 Aromatic ring-containing trialkoxy silanes such as aminobenzyltrimethoxysilane, 4-dimethylaminobenzyltrimethoxysilane and 4-acetylaminobenzyltrimethoxysilane;

Butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- (methoxyethoxy) silane, methyltris (methoxyethoxy) silane, methyltris (methoxyethoxy) silane, methyltriisopropoxysilane, methyltriethoxysilane, , Methyltris (methylethylketoxime) silane, methyltris (trimethylsiloxy) silane, methylsilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriiso- Butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, ethylbistris (trimethylsiloxy) silane, ethyldichlorosilane, Ethyltriacetoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, n-propyltrimethoxysilane, Propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-sec-butoxysilane, n- N-propyltriacetoxysilane, n-propyltrichlorosilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, iso-propyltriethoxysilane, iso- Propyl tri-n-butoxysilane, iso-propyl tri-sec-butoxysilane, iso-propyl tri-tert- Propyltriethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisiso-propoxysilane, n -Butyltrimethoxysilane, n-butyltrimethoxysilane, n-butyltrimethoxysilane, n-butyltrimethoxysilane, n-butyltrimethoxysilane, Propyltrimethoxysilane, 2-methylphenyl Sec-butoxy silane, 2-methylpropyl tri-n-butoxysilane, 2-methylpropyl tri-n-propoxysilane, Butoxysilane, 2-methylpropyltrimethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltriethoxysilane, Propoxy silane, 1-methyl propyl tri-iso-propoxy silane, 1-methyl propyl tri-n-butoxy silane, Propyltriethoxysilane, tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane, tert-butyltriiso- propoxysilane, sec-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltriethoxysilane, tert-butyltrimethoxysilane, tert- Butyldichloro Alkyltrialkoxysilanes such as silane;

Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, -Butoxy silane, vinyltriphenoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltriisopropoxysilane, allyltri-n-butoxysilane, allyltri- and alkenyltrialkoxysilanes such as-sec-butoxysilane, allyltri-tert-butoxysilane and allyltriphenoxysilane.

Among them, from the viewpoints of reactivity and easiness of handling of materials, it is preferable to use 4-methylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane methyltrimethoxysilane, methyltrimethoxysilane Methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriiso- N-butoxysilane, ethyltri-n-propoxysilane, ethyltri-isopropoxysilane, ethyltri-n-butoxysilane, ethyltri- Propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-butyltriethoxysilane, , Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane and the like are preferable.

Specific examples of the compound (2) represented by the above formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra- n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane and tetrachlorosilane.

Among these, tetramethoxysilane and tetraethoxysilane are preferable because an inversion pattern excellent in dry etching resistance can be obtained.

The polysiloxane [A] is preferably obtained by hydrolysis and condensation of the compound (1) and the compound (2). Preferred examples of the compound (1) and the compound (2) include the compounds exemplified above.

As the hydrolyzable silane compound for obtaining the polysiloxane [A], a hydrolyzable silane compound represented by the following formula (5) (hereinafter, also referred to as "compound (5)") may be used in addition to the compounds (1) May be used in combination.

&Lt; Formula (5) >

(5), R ² and R ⁵ each independently represents a hydrogen atom, a fluorine atom, an alkoxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group or an alkylcarbonyloxy group . R ³ are each a monovalent organic group independently. R ⁴ is an aryl group, a methylene group, or an alkylene group having 2 to 10. R ⁴ a may be the same or different from each other if the plurality of presence. b is An integer of 0 to 3, and m is an integer of 1 to 20)

Examples of the alkoxyl group represented by R ² and R ⁵ in the above formula (5) include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n- N-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n -Nonyloxy group, and n-decyloxy group.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. In addition, some or all of hydrogen atoms contained in these alkyl groups may be substituted with a fluorine atom or the like.

Examples of the cyanoalkyl group include a cyanoethyl group and a cyanopropyl group.

Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.

Examples of the monovalent organic group represented by R ^{3 in the} above formula (5) include groups having a cyclic ether structure such as an alkyl group, an alkoxyl group, an aryl group, an alkenyl group and a glycidyl group. Of these, an alkyl group, an alkoxyl group and an aryl group are preferable.

Examples of the alkyl group include a linear or branched alkyl group having 1 to 5 carbon atoms and examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R ² and R ⁵ include . In addition, some or all of hydrogen atoms contained in these alkyl groups may be substituted with a fluorine atom or the like.

The alkoxyl group includes a linear or branched alkoxyl group having 1 to 10 carbon atoms. Specifically, the same groups as exemplified for the alkoxyl group represented by R ² and R ⁵ are exemplified. Examples of the aryl group include phenyl, naphthyl, methylphenyl, benzyl, phenethyl, ethylphenyl, chlorophenyl, bromophenyl, and fluorophenyl groups. Among them, a phenyl group is preferable.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a 3-butenyl group, a 3-pentenyl group and a 3-hexenyl group.

Further, each may be the same or different, a plurality of R ⁴ if R ⁴ is a plurality of presence.

The arylene group in R ⁴ of the above formula (5) is preferably an arylene group having 6 to 10 carbon atoms. Examples thereof include a phenylene group, a naphthylene group, a methylphenylene group, an ethylphenylene group, a chlorophenylene group, a bromophenylene group, and a fluorophenylene group.

Examples of the alkylene group having 2 to 10 carbon atoms include an ethylene group, a propylene group, and a butylene group.

B in the formula (5) is an integer of 0 to 3, preferably 1 or 2.

Further, m is an integer of 1 to 20, preferably 5 to 15, and more preferably 5 to 10.

Specific examples of the compound (5) include hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy- Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2- 1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy- 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2- 2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy- , 2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyldisilane,

1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy- 1,2,2-trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyl di Silane, 1,1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2- Triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2 -Tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-tetramethyldisilane, 1,2 -Dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2 , 2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 2-diphenoxy-1,1,2,2-tetraphenyldisilane;

(Tri-n-butoxysilyl) methane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis ) Methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2- Ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri- Bis (tri-sec-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane (Di-n-propoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- Butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-isopropoxysilyl) methane, 1- -sec-butoxymethylsilyl) -1- (tri- butoxymethylsilyl) -1- (tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) methane, 1- Ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (Di-isopropoxymethylsilyl) -2- (tri-isopropoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (Di-tert-butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1-

Bis (di-n-propoxymethylsilyl) methane, bis (di-isopropoxymethylsilyl) methane, bis (di- (Di-sec-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis Bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, (Di-sec-butoxymethylsilyl) ethane, bis (dimethylmethoxysilyl) ethane, 1,2-bis (Dimethyl-isopropoxysilyl) methane, bis (dimethyl-n-butoxysilyl) methane, bis (dimethyl-sec-propoxysilyl) methane, bis -Butoxysilyl) methane, bis (dimethyl-tert-butoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) Bis (dimethyl-isopropoxysilyl) ethane, 1,2-bis (dimethyl-n-propoxysilyl) ethane, (Dimethyl-sec-butoxysilyl) ethane, 1,2-bis (dimethyl-sec-butoxysilyl) ethane,

1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) (Trimethylsilyl) methane, 1- (di-isopropoxymethylsilyl) -1- (trimethylsilyl) methane, 1- 1- (trimethylsilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (dimethoxymethylsilyl) -2- (Trimethylsilyl) ethane, 1- (diethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (Trimethylsilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- ( (Trimethylsilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (trimethylsilyl) ethane,

Bis (triethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis Bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-tert-butoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, Bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-n-butoxysilyl) benzene, Bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) Benzene, 1,4-bis (tri-isopropoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, , And 4-bis (tri-tert-butoxysilyl) benzene.

Further, polycarbosilanes such as polydimethoxymethylcarbosilane and polydiethoxymethylcarbosilane, and the like can be given.

Among these compounds, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2 -Dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2- Diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2 Bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (Diethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (trimethoxysilyl) ethane, Dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl Bis (dimethylethoxysilyl) methane, 1,2-bis (dimethyl methoxysilyl) ethane, 1,2-bis (dimethylethoxysilyl) ethane, 1- (Dimethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (Trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethylsilyl) (Triethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, polydimethoxymethylcarbosilane , And polydiethoxymethylcarbosilane are preferable.

The compound (5) may be used alone or in combination of two or more.

In addition, the [A] polysiloxane may be contained in only one type or two or more kinds in the resin composition of the present invention.

The molecular weight of the [A] polysiloxane is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 2,000 to 30,000 in terms of polystyrene reduced weight average molecular weight by size exclusion chromatography.

In this specification, the molecular weight of the polysiloxane [A] used in this specification was GPC column (trade name "G2000HXL ", trade name" G3000HXL ", trade name "G4000HXL" Min, elution solvent: tetrahydrofuran, column temperature: 40 占 폚, by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard.

<Synthesis method of [A] polysiloxane>

The method for synthesizing [A] the polysiloxane of the present invention is not particularly limited as long as it is capable of hydrolyzing and condensing at least one compound selected from the compounds (1) and (2), and examples thereof include compounds (1) , Compound (5) or the like, if necessary, in an organic solvent, and this solution and water are intermittently or continuously mixed and hydrolyzed and condensed in the presence of a catalyst at a temperature of usually 0 to 100 ° C to obtain [A] . At this time, the catalyst may be dissolved or dispersed in the organic solvent in advance, or may be dissolved or dispersed in the added water.

The organic solvent used when synthesizing the [A] polysiloxane is not particularly limited as long as it is a solvent used in this kind of application. For example, the same organic solvent as the [B] organic solvent described later can be mentioned as an example. Examples of the catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, inorganic bases and the like. Among these, metal chelate compounds, organic acids and inorganic acids are preferable.

The proportion of the compound (1) in the entire hydrolyzable silane compound is preferably 1 to 99 mol%, more preferably 10 to 95 mol%, particularly preferably 20 to 90 mol%. The proportion of the compound (2) is preferably 1 to 99 mol%, more preferably 5 to 90 mol%, and particularly preferably 10 to 80 mol%. By using the compounds (1) and (2) in the above ratio, it is possible to provide a resin composition which is easy to planarize to expose the surface of a coating film by dry etching using a fluorine-based gas, has excellent dry etching resistance, Can be obtained. The proportion of the compound (5) is preferably 0 to 50 mol%.

<[B] Organic solvent>

[B] The organic solvent includes the compound represented by the above formula (3). [A] It is not particularly limited as long as it is an organic solvent that can dissolve polysiloxane and does not dissolve a mask pattern formed in advance on a substrate to be processed.

In the formula (3), R 'is a straight or branched alkyl group having 1 to 10 carbon atoms. R "is a hydrogen atom or a straight or branched alkyl group having 1 to 9 carbon atoms, provided that the total number of carbon atoms of R 'and R" is 4 to 10.

The compound (3) is an alkyl alcohol or alkyl ether having 4 to 10 carbon atoms. Examples of the linear or branched alkyl group represented by R 'and R "include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. Is in the range of 4 to 10, and preferably in the range of 4 to 8.

Examples of the compound (3) include aliphatic alcohols such as 1-butanol, 2-butanol, 2-methyl-1-propanol, And alkyl alcohols such as ethyl-1-butanol, 2,4-dimethyl-3-pentanol, 4-methyl-2-pentanol, , 2-butanol, 4-methyl-2-pentanol, 3-methyl-2-pentanol and 2-methyl-2-propanol are preferred. Examples of the organic solvent include dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, diisobutyl ether, dibutyl ether, diisobutyl ether, tert- butyl ether, tert-butyl propyl ether, di-tert-butyl ether and dipentyl ether. Of these, diisobutyl ether and dibutyl ether are preferable. The compound (3) may be used alone or in combination of two or more.

[B] The organic solvent may be used for mixing the compound (3) with another solvent. Examples of the other solvent include monohydric alcohols other than the compound (3), polyhydric alcohols, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ethers other than the compound (3) , High-grade hydrocarbons, aromatic hydrocarbons, ketones, esters, fluorine-based solvents, water and the like.

Examples of the monohydric alcohols other than the compound (3) include alcohols such as methanol, ethanol, n-propanol, iso-propanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, Phenylmethylcarbinol, diacetone alcohol, cresol, and the like.

Examples of the polyhydric alcohols include ethylene glycol, propylene glycol and the like.

Examples of alkyl ethers of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like.

Examples of the alkyl ether acetates of polyhydric alcohols include ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate and the like.

Examples of the ether other than the compound (3) include cyclopentylmethyl ether, cyclohexylmethyl ether, cyclopentylethyl ether, cyclohexylethyl ether, cyclopentylpropyl ether, cyclopentyl-2-propyl ether, cyclohexylpropyl ether, Butyl ether, cyclohexyl butyl ether, cyclohexyl-tert-butyl ether and the like.

Examples of the cyclic ethers include tetrahydrofuran and dioxane.

Examples of the higher hydrocarbons include decane, dodecane, undecane, and the like. Examples of the aromatic hydrocarbons include benzene, toluene, and xylene.

Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone.

Examples of esters include ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, Methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate.

Examples of the fluorine-based solvent include perfluoroalkane or perfluorocycloalkane such as perfluorohexane and perfluoroheptane, perfluoroalkane having a double bond in a part of these, and perfluorotetrahydrofuran , And perfluoro cyclic ethers such as perfluoro-2-butyltetrahydrofuran, perfluoroalkanes such as perfluorocyclobutylamine, perfluorotetrapentylamine, and perfluorotetrahexylamine. .

Of these, preferred are monohydric alcohols, ethers, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, and higher hydrocarbons.

The proportion of other solvents that can be mixed is preferably 30 mass% or less, more preferably 20 mass% or less, based on the total amount of the mixed solvent. If it is 30% by mass or more, a problem of mixing with the coating film occurs, which is not preferable.

&Lt; [C] Curing accelerator >

It is preferable that the polysiloxane resin composition of the present invention further contains a [C] curing accelerator in addition to the [A] polysiloxane and [B] organic solvent as essential components. Examples of the curing accelerator include an acid generator (hereinafter also referred to as an " acid generator ") that generates an acid by irradiation and heating of ultraviolet light, or a base generating compound that generates a base by irradiation of ultraviolet light Hereinafter also referred to as "base generator") is preferable. By adding these curing accelerators, the curing of the polysiloxane embedded in the gap of the mask pattern proceeds even at a low temperature, so that the firing condition after the filling can be relaxed. That is, the curing of the polysiloxane is promoted while suppressing the thermal deformation of the mask pattern, whereby the transfer shape can be kept better.

Examples of the acid generator include a compound capable of generating an acid by conducting a heat treatment (hereinafter, also referred to as a "thermal acid generator"), a compound generating an acid by conducting ultraviolet light irradiation treatment (hereinafter, also referred to as " .

The thermal acid generator is a compound which generates an acid by heating usually at 50 to 450 ° C, preferably 200 to 350 ° C. For example, onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts and phosphonium salts.

Specific examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenyl (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro 4-acetoxyphenylsulfonium hexafluoroantimonate and the like;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl- 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Benzylsulfonium salts such as hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzoin tosylate and 2-nitrobenzyltosylate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl -4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl- dibenzylsulfonium salts such as tert-butylphenylsulfonium hexafluoroantimonate and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl P-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzylsulfonium salts such as o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Specific examples of the benzothiazolium salts include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3- (p- 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate, and other benzyl compounds such as benzylthiazolium hexafluoroantimonate, Benzothiazolium salts.

As the other thermal acid generators, 2,4,4,6-tetrabromocyclohexadienone may be exemplified.

Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate , Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate, and the like are preferably used do. Examples of commercially available products include San-aid SI-L85, SI-L110, SI-L145, SI-L150 and SI-L160.

The photoacid generator is a compound which generates an acid by irradiation with ultraviolet light of usually 1 to 100 mJ / cm ² , preferably 10 to 50 mJ / cm ² .

Examples of the photoacid generator include diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium pyrenesulfonate, diphenyl iodonium dodecylbenzenesulfonate, diphenyl iodonium nonafluoro-n- (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium dodecylbenzenesulfonate, bis Iodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium nonafluoro-n-butanesulfonate, triphenylsulfonium iodonium naphthalenesulfonate, bis (4- Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, (hydroxyphenyl) benzenemethylsulfonium toluene Sulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium Reflow Luo methane sulfonate, dicyclohexyl (2-oxo cyclohexyl) sulfonium methane sulfonate, trifluoroacetate,

Dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfo Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano- -Nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyl-diethylsulfonium tri 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthylsulfonium trifluoromethanesulfonate, Butyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetate Methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-naphthyltetrahydrothiophenium trifluoroacetate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, Methanesulfonate, methanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoro 4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfate 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethane sulphate Phonate,

4-isopropoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfate 4-tert-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium tri Fluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoro Onium salt-based photoacid generators such as 1- (naphthyl acetomethyl) tetrahydrothiophenium trifluoromethanesulfonate;

Containing compounds such as phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine and naphthyl-bis (trichloromethyl) Photo acid generator;

1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,3,4,4'-tetrabenzophenone 1,2- Diazo ketone compound-based photoacid generators such as toquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester;

Sulfonic acid compound-based photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane;

Benzotintosylate, tris trifluoromethanesulfonate of pyrogallol, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept- Sulfonic acid compound-based photoacid generators such as 2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethane sulfonate, and 1,8-naphthalene dicarboxylic acid imidotrifluoromethane sulfonate; .

These acid generators may be used alone or in combination of two or more.

The content of the acid generator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the solid content of the polysiloxane [A].

Examples of the base generator include, but are not limited to, triphenylsulfonium compounds, triphenylmethane; Photoactive carbamates such as benzyl carbamate and benzoin carbamate; amides such as o-carbamoyl hydroxyl amide, o-carbamoyl oxime, aromatic sulfonamides, alpha-lactam and N- (2-allylethynyl) amide; Oxime ester,? -Aminoacetophenone, cobalt complex and the like.

Among them, a photobase generator (F1) represented by the following formula (f1); (2-nitrobenzyloxycarbonyl) pyrrolidine, bis [[(2-nitrobenzyl) cyclohexylcarbamate, -Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine; (F2) a carbamate-based photobase generator; Carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1- Benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, hexamine cobalt (III) tris (triphenylmethyl borate) The photo-base generator (F1) and the photo-base generator (F2) are more preferably used, and the photo-base generator (F1) is particularly preferably used.

&Lt; Formula (f1) >

In the above formulas, R ⁴¹ to R ⁴³ each independently represent an alkyl group, an alkoxy group or a halogen atom; n ¹ to n ³ each independently represent an integer of 0 to 3;

In the above formula (f1), the alkyl group represented by R ⁴¹ to R ⁴³ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, more preferably a methyl group, And tert-butyl group are particularly preferable.

The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a straight-chain or branched alkoxy group, and particularly preferably a methoxy group or an ethoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom is most preferable.

In the above formula (f1), n ¹ to n ³ are each independently an integer of 0 to 3, and preferably each independently 0 to 1. Among them, it is more preferable that all of n ¹ to n ³ are 0.

A specific example of the photobase generator (F1) is a compound represented by the following formula (f1-1).

&Lt; Formula (f1-1) >

Among the photobase generator (F2), 2-nitrobenzylcyclohexylcarbamate is most preferable in view of the effects of the present invention. These acid generators may be used alone or in combination of two or more. The content of the acid generator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the solid content of the polysiloxane [A].

In addition to the [A] polysiloxane and [B] organic solvent as an essential component, the [C] curing accelerator as a preferable component, the polysiloxane resin composition of the present invention may contain a surfactant, a crosslinking agent and the like as optional components.

&Lt; Process for producing the polysiloxane resin composition &

The polysiloxane resin composition of the present invention can be prepared by mixing the necessary components [A] polysiloxane and [B] organic solvent, the preferred component [C] curing accelerator, and further optionally, the above optional components. At this time, the solid content concentration of the [A] polysiloxane can be appropriately adjusted, and it is preferably 1 to 30 mass%, more preferably 1 to 20 mass%.

Example

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these embodiments at all. In the description of this embodiment, the description of "part" and "%" is based on mass unless otherwise specified.

<Synthesis of [A] polysiloxane>

A polysiloxane was synthesized as shown in the following Synthesis Examples and Comparative Synthesis Examples. The weight average molecular weight (Mw) of the polysiloxane obtained in each Synthesis Example was measured by the following method.

[Measurement of weight average molecular weight (Mw)] [

And using a GPC column (trade name "G2000HXL ", trade name" G3000HXL ", trade name "G4000HXL" Was measured by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard under the analytical conditions of &lt; RTI ID = 0.0 &gt;

[Synthesis Example 1]

0.53 g of a 20% aqueous solution of maleic acid and 34.89 g of ultrapure water were added to the quartz third-aid flask and heated to 65 占 폚. Next, a solution obtained by mixing 6.42 g of tetramethoxysilane, 51.68 g of methyltrimethoxysilane and 6.48 g of propylene glycol monoethyl ether was added dropwise to the reaction vessel over one hour, and the mixture was stirred at 65 ° C for 4 hours. This solution was cooled to room temperature and concentrated under reduced pressure until the solid content became 25% to obtain a reaction product (polysiloxane A-1). The molecular weight (Mw) of the obtained product was 8,200.

[Synthesis Example 2]

0.54 g of a 20% aqueous solution of maleic acid and 35.25 g of ultrapure water were added to a quartz third-aid flask and heated to 55 캜. Next, a solution obtained by mixing 28.72 g of tetramethoxysilane, 25.70 g of methyltrimethoxysilane and 9.79 g of propylene glycol monopropyl ether was added dropwise to the reaction vessel over 1 hour, and the mixture was stirred at 55 ° C for 3 hours. This solution was cooled to room temperature and concentrated under reduced pressure until the solid content became 25% to obtain a reaction product (polysiloxane A-2). The molecular weight (Mw) of the obtained product was 10,000.

[Synthesis Example 3]

0.54 g of a 20% aqueous solution of maleic acid and 35.25 g of ultrapure water were added to a quartz third-aid flask and heated to 55 캜. Next, a solution obtained by mixing 49.58 g of tetramethoxysilane, 4.93 g of methyltrimethoxysilane and 7.24 g of propylene glycol monoethyl ether was added dropwise to the reaction vessel over 1 hour, and the mixture was stirred at 55 ° C for 3 hours. The solution was cooled to room temperature and concentrated under reduced pressure until the solid content became 25% to obtain a reaction product (polysiloxane A-3). The molecular weight (Mw) of the obtained product was 12,000.

[Synthesis Example 4]

0.54 g of a 20% aqueous solution of maleic acid and 35.25 g of ultrapure water were added to a quartz third-aid flask and heated to 55 캜. Next, a solution obtained by mixing 55.34 g of tetrachlorosilane, 4.93 g of methyltrimethoxysilane, 3.62 g of methanol and 3.62 g of propylene glycol monoethyl ether was added dropwise to the reaction vessel over 1 hour, and the mixture was stirred at 55 ° C for 3 hours . This solution was cooled to room temperature and concentrated under reduced pressure until the solid content became 25% to obtain a reaction product (polysiloxane A-4). The molecular weight (Mw) of the obtained product was 12,000.

[Synthesis Example 5]

0.46 g of a 20% aqueous solution of maleic acid and 29.78 g of ultrapure water were added to a quartz third-aid flask and heated to 55 캜. Next, a solution prepared by mixing 3.38 g of tetramethoxysilane, 12.11 g of methyltrimethoxysilane, 39.41 g of bistriethoxysilylethane and 17.38 g of propylene glycol monoethyl ether was added dropwise to the reaction vessel over 1 hour, Lt; / RTI &gt; for 2 hours. This solution was cooled to room temperature and concentrated under reduced pressure until the solid content became 25% to obtain a reaction product (polysiloxane A-5). The molecular weight (Mw) of the obtained product was 4,000.

[Synthesis Example 6]

To a flask containing 14.59 g of a 25% tetraammonium hydroxide aqueous solution, 4.53 g of water and 40.0 g of methanol was added a cooling tube, 10.66 g of tetramethoxysilane, 1.06 g of 4-methylphenyltrimethoxysilane, methyltrimethoxysilane 3.41 g and 50.00 g of methanol were set in a dropping funnel. Next, after heating to 60 DEG C in an oil bath, the methanol solution of the monomer was slowly dropped and reacted at 60 DEG C for 2 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool.

Thereafter, to the solution obtained by mixing 23.83 g of the 20% aqueous solution of maleic anhydride and 18.73 g of methanol, the reaction solution cooled as described above was added dropwise and stirred for 30 minutes. Next, 450 g of 4-methyl-2-pentenone was added and the mixture was set in an evaporator. The reaction solvent and methanol produced by the reaction were removed to obtain a 4-methyl-2-pentenone solution of the reaction product. The resulting solution was transferred to a separating funnel, followed by addition of 80 g of water, followed by washing with water for the first time, followed by addition of 40 g of water, followed by washing with water for the second time. Thereafter, 370 parts of 4-methyl-2-pentanol was added to the 4-methyl-2-pentenone solution transferred from the separatory funnel to the flask, and the mixture was set in an evaporator to remove 4-methyl- To obtain a 4-methyl-2-pentanol solution of the product (polysiloxane A-6).

[Synthesis Example 7]

0.42 g of maleic anhydride was dissolved by heating in 2 g of water to prepare an aqueous maleic acid solution. Next, 30.5 g of methyltriethoxysilane and 50.8 g of 4-methyl-2-pentanol were placed in a flask. A dropping funnel containing a cooling tube and a previously prepared aqueous solution of maleic acid was set in the flask and heated to 100 ° C in an oil bath. The aqueous solution of maleic acid was slowly added dropwise and reacted at 100 ° C for 4 hours. This solution was cooled to room temperature and concentrated under reduced pressure to a solid content concentration of 25% to obtain a reaction product (polysiloxane A-7). The molecular weight (Mw) of the obtained product was 1,400.

&Lt; Preparation of polysiloxane resin composition >

[Examples 1 to 9, Comparative Example 1]

The polysiloxane resin compositions (J-1 to J-9, j-1) were prepared by mixing the [A] polysiloxane and the [C] curing accelerator obtained in Synthesis Example in the ratios shown in Table 1. An organic solvent [B] was added so that the solid content concentration of each composition was the value shown in Table 1. Further, the content ratio of the organic solvent [B] is the mass ratio.

Details of the [B] organic solvent and the [C] curing accelerator in Table 1 are as follows.

<[B] Organic solvent>

B-1: 4-methyl-2-pentanol

B-2: 1-Butanol

B-3: Dibutyl ether

B-4: Diisoamyl ether

B-5: Propylene glycol monoethyl ether

&Lt; [C] Curing accelerator >

C-1: Triphenylsulfonium trifluorosulfonate

C-2: 2-Nitrobenzylcyclohexylcarbamate

C-3: 4-Acetoxyphenyldimethylsulfonium hexafluoroarsenate

&Lt; Performance evaluation > [Examples 10 to 22 and Comparative Example 2]

Using the respective polysiloxane resin compositions, the following performance evaluations were carried out under the conditions shown in Table 2. The evaluation results are shown in Table 2.

[Intermixability]

A radiation sensitive resin composition solution (AR230JN, manufactured by JSR Corporation) was applied to the surface of a silicon wafer by a spin coater and then dried on a hot plate at 126 占 폚 for 90 seconds to obtain a substrate having a coating film with a thickness of 170 nm. Next, a polysiloxane resin composition for each pattern was coated on the coating film and dried on a hot plate at 120 DEG C for 60 seconds, and then the film thickness of the coating film was measured by a spectroscopic ellipsometer. &Quot; x "indicating that the film thickness was smaller than the initial film thickness and that the film thickness was reduced, and the intermixability with the above coating film was evaluated.

[Filling property between mask patterns]

An antireflection film material (ARC29, manufactured by Nissan Chemical Industries, Ltd.) was coated on the surface of a silicon wafer by a spin coater and then dried on a hot plate at 205 DEG C for 1 minute to form an anti-reflection film (lower film) Was used as a substrate. Next, a radiation-sensitive resin composition (manufactured by JSR Corporation, AR230JN) was coated on the antireflection film and dried at 126 DEG C for 90 seconds. The film thickness of the obtained coating film was controlled at 205 nm. Then, an ArF excimer laser (wavelength: 193 nm) was formed on a quartz reduction projection mask for forming a 1: 1 line-and-space pattern of 0.100 탆 using an ArF excimer laser irradiation apparatus (Nikon Corporation, S306C) And the substrate on which the coated film was formed was irradiated with ¹⁷ mJ / cm ² . Next, the substrate was heated at 126 占 폚 for 90 seconds. Thereafter, development processing was performed with a 2.38% tetramethylammonium hydroxide aqueous solution for 40 seconds to obtain a 1: 1 line-and-space mask pattern having a height of 73 nm and a height of 0.100 mu m on the substrate. Next, each polysiloxane resin composition was applied to the gap between the mask pattern and the mask pattern using a spin coater and dried for 1 minute on a hot plate at a temperature (PEB (占 폚) shown in Table 2) Thereby forming a resin film. With respect to Examples 16 and 18, an ArF excimer laser (wavelength: 193 nm) was irradiated onto the entire surface of a 50 mJ / cm ² wafer using an ArF excimer laser irradiation apparatus (Nikon Corporation, S306C) after drying on a hot plate. The cross section of the thus obtained substrate was observed with a scanning electron microscope (SEM), and the case in which each polysiloxane resin composition was filled in between the mask patterns was shown as "o" Thus, the filling property of the mask pattern was evaluated.

[Dry etching resistance]

The pattern anti-exclusive resin film formed as described above was dry-etched at 500 W for 15 seconds using a barrel-shaped oxygen plasma ashing apparatus "PR-501" (manufactured by Yamato Chemical Co., Ltd.). The difference between the film thickness of the pattern antireflection resin film before the treatment and the film thickness of the pattern antireflection resin film after the treatment was determined and evaluated as dry etching resistance. In addition, it is evaluated that the dry etching resistance is better as the film thickness variation width is smaller.

[Storage stability]

The polysiloxane resin composition for each pattern was coated on the surface of the silicon wafer under the conditions of a rotation number of 2,000 rpm and a speed of 20 seconds using a spin coater and then dried on a hot plate at 120 캜 for one minute to obtain a pattern anti- . Next, with respect to the obtained pattern anti-reflection resin film, the film thickness was measured at nine points using an optical film thickness meter (manufactured by KLA-Tencor, model number "UV-1280SE") and the average film thickness thereof was obtained. After each composition was stored at 40 占 폚 for one week, a resin film was formed in the same manner as above to measure the film thickness, and the average film thickness thereof was determined. Next, the difference (T-T0) between the average film thickness T0 of the resin film before storage and the average film thickness T of the pattern antireflection resin film after storage is obtained and the difference The ratio [(T-T0) / T0] was calculated as the film thickness increase rate. Further, it is evaluated that the smaller the film thickness increase rate is, the better the storage stability is. The film thickness increase rate is 5.5% or less in practical use, although it is practically acceptable, but it is more preferably 5% or less.

[Measurement of content of silicon and carbon]

Each composition was coated on the surface of a silicon wafer under the conditions of a rotation speed of 2000 rpm and a speed of 20 seconds by using a spin coater and then dried on a hot plate at 200 캜 for one minute to form a resin film. The content of silicon (Si) and carbon (C) in the resin film was measured using SIMS (PHI ADEPT-1010 manufactured by ULVAC-PHI Co.), and the average value of the measured values in the depth direction was calculated, did.

&Lt; Formation of reversal pattern >

[Example 23]

An inversion pattern was formed using the polysiloxane resin composition of Example 1 of the present invention. Will be described with reference to Fig.

An antireflection film material (ARC29, manufactured by Nissan Chemical Industries, Ltd.) was coated on the surface of a silicon wafer by a spin coater and then dried on a hot plate at 205 DEG C for 1 minute to form an anti-reflection film (lower film) Was used as a substrate.

Next, a radiation-sensitive resin composition (AR230JN, manufactured by JSR Corporation) was coated on the antireflection film and dried at 126 占 폚 for 90 seconds. The film thickness of the obtained coating film was controlled at 205 nm. Thereafter, an ArF excimer laser (wavelength: 193 nm) was formed on a substrate having the coating film formed thereon through a quartz mask for forming a 1: 1 line-and-space pattern of 0.100 mu m using an ArF excimer laser irradiation apparatus (Nikon Corporation) ¹⁷ mJ / cm ² . Next, the substrate was heated at 126 占 폚 for 90 seconds. Thereafter, development processing was performed with a 2.38% tetramethylammonium hydroxide aqueous solution for 40 seconds to obtain a mask pattern of 1: 1 line-and-space of 0.100 m on the substrate as shown in Fig. 1 (b).

Next, the resin composition for reversal pattern formation of Example 1 was applied to the gap between the mask pattern and the mask pattern by a spin coater at a rotation number of 150 nm, baking treatment at 160 DEG C for 1 minute , A resin film as shown in Fig. 1 (c) was formed. At this time, the film thickness of the reversed pattern forming resin was 210 nm.

Thereafter, the surface of the resin film was dry-etched using a plasma containing a mixed gas of CF ₄ / O ₂ in the RIE apparatus. The etching was carried out until the surface of the mask pattern 31 was exposed (dry etched back) as shown in Fig. 1 (d). As a result, as shown in Fig. 1 (d), it was possible to leave a reversed pattern forming resin film only in the gap of the mask pattern 31. [

Further, dry etching was performed using a plasma containing a mixed gas of N ₂ / O ₂ in the RIE apparatus to obtain a reversed pattern as shown in FIG. 1 (e). At this time, the height dimension of the inverted pattern was about 180 nm, and it was a rectangular shape.

&Lt; Formation of microinverted pattern >

[Example 24] Double exposure method

A 12-inch silicon wafer on which a lower antireflection film "ARC66" (manufactured by Brewer Science) having a thickness of 105 nm was formed on the surface of a silicon wafer was used. "ARX2014J" (manufactured by JSR Corporation) was coated on the antireflection film using "CLEAN TRACK ACT12" (manufactured by Tokyo Electron Co., Ltd.) and dried at 90 ° C for 60 seconds. The film thickness of the resist at this time was controlled to be 100 nm. Furthermore, a liquid immersion upper layer film material "NFC TCX091-7" (manufactured by JSR Corporation) was applied onto the formed resist film and dried at 90 DEG C for 60 seconds. The film thickness of the liquid immersion upper layer film at this time was controlled to 30 nm. Thereafter, the first exposure was performed under a condition of 16 mJ / cm ² through a quartz mask for forming a 1: 1 line-and-space pattern of 40 nm using an ArF excimer laser irradiation apparatus "S610C" (Nikon Corporation). Next, the quartz mask was rotated by 90 degrees so that a latent image of the mask was obtained in a direction perpendicular to the latent image obtained by the first exposure, and the second exposure was performed at 16 mJ / cm ² . Subsequently, the substrate was heated at 115 캜 for 60 seconds, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds to form a filler mask pattern having a height of 85 nm and a columnar diameter of 40 nm.

Next, a polysiloxane resin composition (J-2) for reversal pattern formation was applied to the gap between the mask pattern and the mask pattern using a spin coater and dried on a hot plate at 120 DEG C for 1 minute, A resin film having a thickness of 150 nm was formed. This substrate was immersed in a 0.5% aqueous solution of tetramethylammonium hydroxide for 30 seconds so that the surface of the previously formed mask pattern was exposed to the surface of the polysiloxane (wet etch-back). Then heated 1 minute at 180 ℃ substrate more cured polysiloxane portion, by using a plasma containing a mixed gas of N ₂ / O ₂ in the RIE apparatus for performing dry etching, to obtain a reverse pattern. At this time, the reversal pattern was a fine hole pattern in which holes having a diameter of about 40 nm were formed at regular intervals.

[Example 25] Double patterning method

A 12-inch silicon wafer on which a lower antireflection film "ARC66" (manufactured by Brewer Science) having a thickness of 105 nm was formed on the surface of a silicon wafer was used. Next, "ARX3520JN" (manufactured by JSR Corporation) was coated on the antireflection film by using "CLEAN TRACK ACT12" (manufactured by Tokyo Electron Co., Ltd.) and dried at 90 ° C. for 60 seconds. The film thickness of the resist at this time was controlled to be 100 nm. Next, using an ArF excimer laser irradiation apparatus "S610C" (manufactured by Nikon Corporation), irradiation was carried out through a quartz mask for pattern formation in a 1: 3 line-and-space pattern of 40 nm under the condition of an exposure dose of 23 mJ / cm ² . Next, the substrate was heated at 105 DEG C for 60 seconds, and developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds to form a first mask pattern having a height of 85 nm and a line width of 40 nm. Next, this mask pattern formation substrate was heated at 150 캜 for one minute to carry out the insolubilization treatment of the first mask pattern.

Next, "ARX3714JN" (manufactured by JSR Corporation) was coated and film-formed on the first mask pattern substrate so as to have a thickness of 105 nm in the same manner as in "ARX3520JN" And then patterned through a quartz mask for pattern formation of the same 40 nm 1: 3 line-and-space shape so that the position of the wafer was shifted by 80 nm on the exposure apparatus so as to form a second mask pattern between the first mask patterns . Subsequently, exposure (20 mJ / cm ² ), heating (60 sec at 100 캜) and development (2.38% aqueous solution of tetramethylammonium hydroxide for 30 seconds) were performed in the same manner as in the first patterning, A 1: 1 line-and-space mask pattern of 40 nm was formed.

A polysiloxane resin composition (J-5) for reversal pattern formation was applied to the gap by a spin coater and dried on a hot plate at 140 占 폚 for 1 minute to form a resin film having a film thickness of 150 nm from the surface of the ARC66. An ArF excimer laser (wavelength: 193 nm) was irradiated onto the entire surface of the wafer at a rate of 50 mJ / cm ² to further cure the polysiloxane resin. Thereafter, the surface of the polysiloxane resin film was dry-etched using a plasma containing a mixed gas of CF ₄ / O ₂ in the RIE apparatus. The etching was carried out until the surface of the mask pattern 31 was exposed (dry etched back) as shown in Fig. 1 (d). Next, dry etching was performed using a plasma containing a mixed gas of N ₂ / O ₂ in the RIE apparatus to obtain an inversion pattern. At this time, the reversal pattern was a fine line pattern in which lines of about 40 nm were formed at regular intervals.

As is apparent from Table 2, the polysiloxane resin composition for pattern reversal of the present example can be favorably embedded between mask patterns formed on the coating film without intermixing with the coating film formed on the substrate, and the dry etching resistance and the storage stability And it was confirmed that it is excellent. In Comparative Example 1, the mask pattern disappeared at the stage of application on the mask pattern.

In Example 23, by using the polysiloxane resin composition of the present invention, it was possible to form a favorable pattern in which lines of 100 nm were formed at equal intervals as an inverted pattern of a conventional mask pattern. Furthermore, from the results of Examples 24 and 25, the polysiloxane resin composition of the present invention is preferably used as an inverted pattern material of a finer mask pattern formed by the double exposure method and the double patterning method, It was found that a good fine line pattern could be formed.

According to the inversion pattern forming method of the present invention, the polysiloxane resin composition of the present invention can be well embedded in the gap of the mask pattern without being mixed with the mask pattern formed on the substrate to be processed, and furthermore, the dry etching resistance and the storage stability Is excellent. Therefore, the present invention can be very advantageously used for the production of LSI which is expected to be further miniaturized in the future, particularly for the formation of fine contact holes and the like.

1: processed substrate 2: antireflection film
3: Coating film 31: Mask pattern
4: pattern anti-reflection resin film 41: reverse pattern

Claims (11)

(1) a mask pattern forming step of forming a mask pattern on a substrate to be processed,
(2) an embedding step of embedding the polysiloxane resin composition in the gap of the mask pattern, and
(3) an inversion pattern forming step of removing the mask pattern to form an inversion pattern
The method comprising the steps of:
Wherein the polysiloxane resin composition comprises:
[A] a polysiloxane obtained by hydrolyzing and condensing at least one member selected from the group consisting of a hydrolyzable silane compound represented by the following formula (1) and a hydrolyzable silane compound represented by the following formula (2), and
[B] an organic solvent containing a compound represented by the following formula (3)
Wherein the reversed pattern forming step comprises:
&Lt; Formula (1) >

(1), R is a hydrogen atom, a fluorine atom, a straight or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group or an aryl group, A halogen atom or -OR ¹ , R ¹ is a monovalent organic group, and a is an integer of 1 to 3, provided that when a plurality of R and X are present, they may be the same or different from each other)
&Lt; Formula (2) >

(In the formula (2), X is synonymous with the above formula (1)).
&Lt; Formula (3) >

(3), R 'is a linear or branched alkyl group having 1 to 10 carbon atoms and R "is a hydrogen atom or a straight or branched alkyl group having 1 to 9 carbon atoms, with the proviso that R' and R "Is 4 to 10) The method of forming an inversion pattern according to claim 1, wherein the [A] polysiloxane is a polysiloxane obtained by hydrolyzing and condensing a hydrolyzable silane compound represented by the formula (1) and a hydrolyzable silane compound represented by the formula (2). The method of forming an inversion pattern according to claim 1, wherein X in the formulas (1) and (2) is -OR ¹ (provided that R ¹ is the same as in the above formula (1)). The method for forming an inversion pattern according to claim 1, wherein the content of silicon atoms is 30% by mass or more and 46.7% by mass or less, and the content of carbon atoms is 1% by mass or more and 50% by mass or less, The method according to claim 1, wherein (1)
(i) a coating film forming step of forming a coating film by applying and drying a radiation-sensitive resin composition on a substrate to be processed,
(ii) an exposure step of irradiating a predetermined region on the coating film with radiation, and
(iii) a developing step of developing the exposed coating film
Gt; pattern. &Lt; / RTI &gt; 6. The method according to claim 5, wherein (ii) the exposure step is performed a plurality of times in succession. 6. The method according to claim 5, wherein (1) the step of forming a mask pattern is repeatedly performed to form a first mask pattern and a step of forming a second mask pattern different from the first mask pattern. A polysiloxane resin composition for use in forming an inverted pattern of a mask pattern formed on a substrate to be processed,
[A] a polysiloxane obtained by hydrolyzing and condensing at least one member selected from the group consisting of a hydrolyzable silane compound represented by the following formula (1) and a hydrolyzable silane compound represented by the following formula (2), and
[B] an organic solvent containing a compound represented by the following formula (3)
&Lt; / RTI > by weight of the polysiloxane resin composition.
&Lt; Formula (1) >

(1), R is a hydrogen atom, a fluorine atom, a straight or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group or an aryl group, A halogen atom or -OR ¹ , R ¹ is a monovalent organic group, a is an integer of 1 to 3, and when a plurality of R 1 and X 2 are present, they may be the same or different from each other)
&Lt; Formula (2) >

(In the formula (2), X is synonymous with the above formula (1)).
&Lt; Formula (3) &gt;

(3), R 'is a linear or branched alkyl group having 1 to 10 carbon atoms and R "is a hydrogen atom or a straight or branched alkyl group having 1 to 9 carbon atoms, with the proviso that R' and R "Is 4 to 10) The polysiloxane resin composition according to claim 8, wherein the [A] polysiloxane is a polysiloxane obtained by hydrolyzing and condensing a hydrolyzable silane compound represented by the formula (1) and a hydrolyzable silane compound represented by the formula (2). The polysiloxane resin composition according to claim 8, wherein the polystyrene reduced weight average molecular weight of the polysiloxane [A] by size exclusion chromatography is 2,000 or more and 100,000 or less. The polysiloxane resin composition according to claim 8, further comprising a [C] curing accelerator.

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